Patent GB-818143-A (GB)
Title: Olefinically unsaturated compounds and polymeric compounds derived therefrom
IPC: C07D303/22
Filed: 1955-10-20
Abstract: The invention comprises homopolymers and copolymers of the monomers of formula <FORM:0818143/IV (a)/1> wherein R is hydrogen or alkyl, m is 0 or 1, Ar is an arylene radical and X is <FORM:0818143/IV (a)/2> in which n=1 to 8 when m=0 and n=2 to 8 when m=1 and in which the unoccupied valencies are satisfied by hydrogen or alkyl groups, a hydroxyalkyl group containing from 1 to 8 carbon atoms CnH2n-1(OH)2, in which n=1 to 8 when m=0 and n=1 to 8 excluding 3 when m=1, a chloroalkyl group containing from 1 to 8 carbon atoms or CH2CONR1R11 in which R1 and R11 are hydrogen, alkyl, aryl or aralkyl (see Group IV (b)).  The polymers obtained may be reacted further with drying oil fatty acids, polyisocyanates and polyoxiranes.  The compounds of the above formula which contain both an alkenyl and an oxirane group may, for example, be polymerized through the alkenyl group using peroxide catalysts to give a linear polymer and then the oxirane group may be reacted, for example by heating or by reaction with cross-linking agents such as polyisocyanates, polyoxiranes, polyols or polyamines to give varying amounts of cross-linking. Alternatively the oxirane group may be polymerized first and the polymer cross-linked through the alkenyl groups.  Specified peroxide catalysts are hydrogen, acetyl, acetylbenzoyl, benzoyl, phthalyl and lauroyl peroxides, tertiary-butyl hydroperoxide, ammonium and sodium persulphates and sodium perchlorate.  In examples: (1) 1-(21-vinylphenoxy)-2 : 3-epoxypropane is heated in a nitrogen atmosphere in the presence of benzoyl peroxide to give a linear soluble polymer containing oxirane oxygen; (2) a mixture of 1-(21-vinylphenoxy)-2 : 3-epoxypropane and styrene is copolymerized by heating in a nitrogen atmosphere in the presence of benzoyl peroxide as catalyst to give a soluble linear heat-curable polymer and the styrene may be replaced by one or more of the following monomers:-methyl-, dimethyl-, chloro-, polychloro- and cyano-styrenes, vinylnaphthalenes, vinyl and vinylidene chlorides, acrylic acid, methyl and ethyl acrylates, acrylonitrile, butadiene and maleic acid and anhydride; (3) a mixture of 1 - (21 - vinylphenoxy) - 2 : 3 - epoxypropane and ethylene oxide is copolymerized by heating in the presence of succinic acid to give a soluble linear copolymer containing oxyethylene linkages and the ethylene oxide may be replaced by propylene, butylene and cyclohexene oxides, butylene dioxide, glycide and the diglycidyl ether of p : p1-dihydroxydiphenyl; (4) the product of (1) is heated to give a solid insoluble polymer; (5) 1-(41-isopropenylphenoxy)-2 : 3-propanediol is treated as in (1) to give a linear soluble polymer; (6) a mixture of 1-(41-isopropenylphenoxy) - 2 : 3 - propanediol, maleic anhydride and benzoyl peroxide is dissolved in xylene and heated, the xylene is removed by vacuum distillation to give a linear soluble copolymer; (7) the product of (5) is mixed with the diglycidyl ether of p : p1-dihydroxydiphenyl and ethylene diamine and heated to give a thermoset resin; (8) 2-(41-allylphenoxy)-ethanol is treated as in (1) to give a linear soluble polymer; (9) a mixture of 2-(41-allylphenoxy)-ethanol and butadiene is treated as in (2) to give a linear soluble copolymer and the butadiene may be replaced by another monomer as in (2); (10) the product of (8) is mixed with linseed fatty acids and heated while passing nitrogen through the mixture to give a modified polymer with greater oil-solubility and the linseed fatty acids may be replaced by acids derived from dehydrated castor, tung, perilla, soybean, oiticica, fish, hempseed, poppy seed and sunflower oils; (11) 2-(21-vinylphenoxy)-1-chloroethane is treated as in (1) to give a linear-soluble polymer; (12) a mixture of acrylonitrile and 2 - (21 - vinylphenoxy) - 1 - chloroethane is treated as in (2) to give a linear soluble copolymer and the acrylonitrile may be replaced by another monomer as in (2); (13) a mixture of p-divinylbenzene and 2-(21-vinylphenoxy)-1-chloroethane is treated as in (2) to give an insoluble infusible copolymer, which is treated with triethylamine to give a resin having quaternary ammonium chloride groups and showing ion-exchange properties; (14) the product of (11) is heated with ethylene diamine to give a thermoset resin and other amines which may be used are the propylene-, hexylene-, phenylene- and naphthylene-diamines; (15) 4-allylphenoxyacetamide is dissolved in xylene and heated in a nitrogen atmosphere in the presence of benzoyl peroxide and the xylene is removed by vacuum distillation to give the homopolymer; (16) a mixture of 4-allylphenoxyacetamide and styrene is treated as in (2) to give a linear-soluble copolymer, the styrene may be replaced by other monomers as in (2) and the 4-allylphenoxyacetamide may be replaced by 2-vinyl-, 3-allyl- or 4-isopropenyl-phenoxyacetamide or mixtures thereof; (17) the product of (16) is reacted with 2 : 4-toluenediisocyanate to give a thermoset resin and other diisocyanates such as 2 : 4- or 2 : 6-phenylene-, 2 : 6-toluene-, 1 : 5-naphthalene-, 4 : 41 - xenylene- and tetramethylene-diisocyanate may be used; (18) the product of (15) is mixed with hexamethylenetetramine and urea or melamine and the mixture cured to give a thermoset resin.ALSO:The invention comprises compounds of formula <FORM:0818143/IV (b)/1> wherein R is hydrogen or alkyl, m is 0 or 1, Ar is an arylene radical and X is <FORM:0818143/IV (b)/2> in which n = 1 to 8 when m = 0 and n = 2 to 8 when m = 1 and in which the unoccupied valencies are satisfied by hydrogen or alkyl groups, a hydroxyalkyl group containing from 1 to 8 carbon atoms, CnH2n-1(OH)2 in which n = 1 to 8 when m = 0 and n = 1 to 8 excluding 3 when m = 1, a chloroalkyl group containing from 1 to 8 carbon atoms, or CH2CONR1R11 in which R1 and R11 are hydrogen, alkyl, aryl or aralkyl; and polymeric compounds derived therefrom (see Group IV (a)).  In examples: (1) a mixture of 2-vinylphenol with sodium hydroxide and water is added to epichlorhydrin with stirring and cooling, the reaction mixture is extracted with ether, the ether is evaporated and the oily residue is distilled to give 1 - (21 - vinylphenoxy) - 2 : 3 - epoxypropane containing minor proportions of 1-(21 - vinylphenoxy) - 2 : 3 - propanediol; further alkenylphenols and epoxyalkanes which may be similarly reacted are 3- or 4-vinylphenol, 3-isopropenylphenol, 2- or 3-allylphenol, the vinyl-, isopropenyl- and allyl-1- or -2-naphthols, 1-chloro-2 : 3-epoxybutane, 1- or 2 - chloro - 3 : 4 - epoxybutane, 1 - chloro - 2 - methyl - 2 : 3 - epoxypropane, 1 - bromo - 2 : 3-epoxypentane, 2 - chloromethyl - 1 : 2 - epoxybutane, 1 - bromo - 4 - methyl - 3 : 4 - epoxypentane, 1 - bromo - 4 - ethyl - 2 : 3 - epoxypentane, 4 - chloro - 2 - methyl - 2 : 3 - epoxypentane, 1 - chloro - 2 : 3 - epoxyoctane, 1 - chloro - 2 - methyl - 2 : 3 - epoxyoctane or 1-chloro - 2 : 3 - epoxydecane; (2) 1 - (41 - isopropenylphenoxy) - 2 : 3 - epoxypropane prepared by reacting 4-isopropenylphenol and epichlorohydrin as in (1) is hydrolysed with aqueous sodium hydroxide to give 1-(41-isopropenylphenoxy)-2 : 3-propanediol, and similar compounds specified are 1-(21- or 31-vinylphenoxy)- or - (41 - isopropenylphenoxy) - 2 : 3 - propanediol and 1 - (21 - alkylphenoxy) - 3 : 4 - butanediol; (3) a mixture of 4-allylphenol, sodium hydroxide and water is added with stirring and cooling to ethylene chlorohydrin, the reaction mixture is extracted with ether, the extract is washed with aqueous sodium hydroxide and evaporated to give 2-(41-allylphenoxy)-ethanol, and similar compounds specified are 2-(21-vinyl- or 41-isopropenylphenoxy)-ethanol, 3-(21 - vinyl - or 41 - isopropenyl - or - allyl - phenoxy)-propanol and 1-(21-vinylphenoxy)-2-propanol; (4) a mixture of 2-vinylphenol, sodium hydroxide and water is added with stirring to 1 : 2-dichloroethane maintained at 75 DEG  C., the water and excess dichloroethane are distilled off, the residue is cooled, extracted with ether, the extract is washed with aqueous sodium hydroxide solution and evaporated to give 2 - (21 - vinylphenoxy) - 1 - chloroethane, and similar compounds specified are 2-(21- or 41-allyl- or 41-isopropenylphenoxy)-1-chloroethane, 2 - (21 - vinylphenoxy) - 1 - chloropropane, and 3-(41 - isopropenylphenoxy)-1-chloropropane; (5) a solution of 4-allylphenoxyacetic acid in toluene is refluxed, ammonia is bubbled in, water is removed by azeotropic distillation and the product distilled to give 4-allylphenoxyacetamide, and similar compounds specified are 2-allyl-, 3-vinyl- and 4-isopropenylphenoxyacetamides; other alkenylaryloxyacetic acids which may be used are 2-vinyl- or 3-allyl-phenoxyacetic acids and allyl-1- or -2-naphthoxyacetic acids and amines which may replace ammonia are methyl-, ethyl-, propyl-, butyl-, decyl-, dimethyl-, dipropyl-, dibutyl- and didecylamines, aniline, methyl- or propylaniline, benzylamine, dibenzylamine, dimethylaminoanilines and N : N-dimethyl-phenyleneamines.  The preparation of the alkenylaryloxyacetic acids used in (5) is illustrated by the preparation of 2-vinylphenoxyacetic acid, wherein a mixture of 2-vinylphenol, sodium hydroxide and water is added to an aqueous solution of sodium bromoacetate, the mixture heated and then acidified with hydrochloric acid to give 2-vinylphenoxyacetic acid.